CN108607365B - Super-hydrophobic nanofiber composite membrane for membrane distillation and preparation method thereof - Google Patents
Super-hydrophobic nanofiber composite membrane for membrane distillation and preparation method thereof Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/04—Hydrophobization
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a super-hydrophobic nanofiber composite membrane for membrane distillation and a preparation method thereof. The nanofiber composite membrane is of a double-layer structure and comprises a base layer and a surface layer which are mutually compounded, wherein the base layer is a nanofiber base membrane, and the surface layer is a porous super-hydrophobic separation layer. The preparation method comprises the following steps: preparing a base layer by adopting a polymer solution electrostatic spinning method, and then carrying out hot pressing treatment; heating and dissolving a polyolefin material in a solvent, uniformly stirring, removing a solvent-rich phase under the external action of a vacuum auxiliary suction filtration method, and depositing a polymer-rich phase on the surface of a base layer; then adding volatile polyolefin non-solvent to construct the nanofiber composite membrane with the porous structure skin layer on the microscopic scale. The product membrane prepared by the invention is efficient and durable, the preparation method is simple and feasible, the defects of high price, low porosity, low water vapor flux and easy wetting of membrane pores of the traditional membrane distillation membrane can be obviously improved, and the large-scale modification of the traditional membrane distillation membrane is easy to realize.
Description
Technical Field
The invention relates to a super-hydrophobic nanofiber composite membrane with a honeycomb structure and prepared by depositing low-surface-energy polyolefin by a vacuum-assisted suction filtration method for membrane distillation and a preparation method thereof, and belongs to the technical field of material engineering.
Background
The pollution and shortage of water resources are the problems generally faced by the present society, the membrane separation technology has been widely applied in the fields of seawater desalination, wastewater treatment and the like as a novel efficient separation, purification and concentration technology, and among numerous membrane separation technologies, membrane distillation is increasingly paid more attention to 2016 and research by its unique advantages (such as availability of low-quality heat source, high rejection rate, simple equipment, mild and convenient operation conditions and the like) [ Wang Z, Hou D, Lin S, environ. Membrane distillation is a membrane separation process using steam pressure difference on two sides of a hydrophobic microporous membrane as a mass transfer driving force [ wuhuile, membrane distillation technology and application progress thereof, membrane science and technology, 2003, 23, 67-79 ]. Considering that the membrane for membrane distillation needs to be contacted with high-temperature brine having strong wettability, the microporous membrane used for membrane distillation should have high hydrophobicity. But is limited by the few kinds of traditional hydrophobic materials and the disadvantages of traditional membrane preparation processes (such as stretching method, phase inversion method, surface modification method, blending modification method and composite membrane method), and the prepared flat membrane and hollow fiber membrane have the defects of low porosity, low hydrophobicity and the like, so that the membrane pores are easy to wet and the water flux is low in the membrane distillation process. These disadvantages severely limit the development and large-scale industrial production applications of membrane distillation commercial membranes.
The nanofiber porous membrane prepared by the electrostatic spinning technology is widely applied to membrane distillation desalination, and has the characteristics of super-large surface area to volume ratio, high porosity, interconnected open pore structure and controllable membrane thickness [ Li D, Xia Y2004 adv. Mater 161151-70; yoon K, Hsiao B S, Chu B2008J. Mater. chem 185326-34 ], can effectively improve the defects that the membrane prepared by the traditional phase inversion method for membrane distillation has small porosity and the formed micropores are closed pore structures, and improve the water vapor flux of the membrane for membrane distillation, but the loose membrane structure also aggravates the problem that the membrane pores are easy to be wetted. Therefore, most of the nanofiber porous membranes prepared by the electrospinning technology need to build surface roughness by virtue of organic/inorganic particles and introduce a hydrophobic modifier with low surface energy, so that the anti-wettability of the nanofiber membrane is improved. These hydrophobic modifiers with low surface energy are expensive and can pollute the environment, which increases the preparation cost of the membrane for membrane distillation and seriously hinders the popularization and application of the membrane distillation technology in the field of seawater desalination.
In recent years, composite membranes prepared by constructing a hydrophobic skin layer on the surface of a porous support membrane by using cheap and easily available low-surface-energy polymer materials are more and more favored by researchers [ Shaulsky E, Nejati S, Boo C, Perreault F, Osuji C O, Elimelech, M2017 J.Membr.Sci 530158-. The polyolefin has the advantages of excellent corrosion resistance, water resistance, good mechanical strength, lower price and the like. The low-surface-energy polyolefin material is deposited on the surface of the nanofiber through a vacuum-assisted suction filtration method, the problem that the low-surface-energy material is difficult to process by a traditional membrane preparation method can be effectively avoided while various advantages of the nanofiber are achieved, the selection range of raw materials is expanded, the super-hydrophobic skin layer with the porous honeycomb structure is prepared, and compared with a traditional phase transition membrane and a common nanofiber membrane, the nanofiber porous membrane with the bionic structure characteristic can endow the separation membrane with more excellent performance. Aiming at the defects of the traditional membrane for membrane distillation, the nanofiber membrane with ultrahigh porosity, large surface area-to-volume ratio and mutually communicated open pore structure is prepared by using an electrostatic spinning method, and fluffy nanofibers are mutually connected to form a complete and uniform nanofiber porous membrane through hot pressing treatment, so that the porosity and the water vapor flux are improved; on the other hand, cheap and easily-obtained polyolefin materials are selected to be dissolved in a solvent at a high temperature and uniformly stirred, the mixture is cooled to different temperatures at a controllable cooling rate, a solvent-rich phase is removed under the external action force of a vacuum-assisted suction filtration method in combination with the principle that the polyolefin solution is in a thermodynamically unstable state and is easy to gel, a polymer-rich phase is deposited on the surface of the nanofiber membrane, and the nanofiber composite membrane with a porous structural skin layer on a microscale is constructed, so that the superhydrophobic property is presented macroscopically, and the anti-wettability problem of the membrane for membrane distillation in the operation process is improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the product membrane prepared by the invention is efficient and durable, the preparation method is simple and feasible, the defects of low porosity, low water vapor flux and easy wetting of membrane pores of the traditional membrane for membrane distillation can be obviously improved, the price cost of superhydrophobic modification of the membrane for membrane distillation is reduced, and the further development of the membrane distillation technology is promoted.
In order to solve the problems, the invention provides a super-hydrophobic nanofiber composite membrane for membrane distillation, which is characterized in that the nanofiber composite membrane is of a double-layer structure and comprises a base layer and a surface layer which are mutually compounded, wherein the base layer is a nanofiber base membrane, and the surface layer is a porous super-hydrophobic separation layer. The porous skin layer with the low surface energy characteristic can effectively resist the infiltration of high-temperature salt solution in the membrane distillation operation process while endowing the nanofiber composite membrane with high porosity, thereby improving the membrane durability and the water vapor flux for the membrane distillation.
Preferably, the porosity of the nanofiber composite membrane is 75-95%, the thickness of the nanofiber composite membrane is 50-300 mu m, the average pore diameter is 0.1-1.5 mu m, the pore size distribution is 0.11-4.0 mu m, the water osmotic pressure is 0.4-3 bar, and the water contact angle is 140-175 degrees.
The invention also discloses a preparation method of the super-hydrophobic nanofiber composite membrane for membrane distillation, which is characterized by comprising the following steps of:
step 1): preparing a base layer by adopting a polymer solution electrostatic spinning method, and then carrying out hot pressing treatment, wherein the temperature of a hot pressing plate is 50-500 ℃, and the pressure is 1 kPa-6 multiplied by 104kPa, and the hot pressing time is 30s to 5h, thereby remelting at the intersection between adjacent fibers to form a connectionThe joints are connected, so that the fluffy nanofiber membrane is complete and uniform;
step 2): preparing a porous super-hydrophobic separation layer: heating and dissolving a polyolefin material in a solvent, uniformly stirring, cooling to different temperatures at a controllable cooling rate, combining the principle that the polyolefin solution is in a thermodynamically unstable state and is easy to gelate, and removing a solvent-rich phase under the external action force of a vacuum-assisted suction filtration method, wherein the polymer-rich phase is deposited on the surface of the base layer obtained in the step 1); stopping suction filtration when no redundant solution exists on the surface of the membrane, adding a volatile polyolefin non-solvent, standing, and suction-filtering off the polyolefin non-solvent to construct a nanofiber composite membrane with a porous structure skin layer on a microscale; the introduction of the polyolefin non-solvent can accelerate the phase separation of the polyolefin, remove the good solvent with high boiling point, keep the pore structure of the separation layer stable and is not easy to block.
Step 3): carrying out heat treatment on the nanofiber composite membrane obtained in the step 2) for 8-24h in an oven with the temperature of 35-80 ℃ and the vacuum degree of-0.09 to-0.1 Mpa.
Preferably, the solute adopted by the polymer solution in step 1) is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyvinyl chloride, polyurethane, polycarbonate, polystyrene, polyacrylonitrile or polyether sulfone, and the solvent is any one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, dichloromethane, trichloromethane, acetone, benzene, toluene, cyclohexane and dimethyl sulfoxide.
Preferably, the specific process parameters of the electrospinning method in the step 1) are as follows: the concentration of the polymer solution is 2-40 wt%, the voltage is 10-35 kV, the extrusion pushing speed of the solution is 2-30 mu L/min, the receiving distance is 10-30 cm, the rotating speed of a receiving roller is 300-1000 r/min, the atmosphere of the spinning environment is a closed or open space system, the relative humidity of the system is 10-40%, and the temperature is 15-45 ℃.
Preferably, the polyolefin material in the step 2) is any one or more of polypropylene (PP), Polyethylene (PE), Polybutylene (PB) and poly-4-methyl-1-pentene (TPX); the solvent is any one or more of dimethylbenzene, normal hexane, cyclohexane, decalin, tetrahydronaphthalene and petroleum ether; the polyolefin non-solvent is any one or more of isopropanol, ethanol, methanol and butanone.
Preferably, the negative pressure adopted by the vacuum auxiliary suction filtration method in the step 2) is-0.09 MPa to-0.1 MPa, and the loading capacity of the polyolefin is 0.1 g/m to 500g/m2。
The porosity is determined gravimetrically.
The pore diameter and pore diameter distribution of the nanofiber porous membrane characterized by a capillary flow pore diameter analyzer, the average flow pore diameter, the gas transmittance and other membrane structure characteristics are adopted.
The vacuum-assisted suction filtration super-hydrophobic nanofiber composite membrane is applied to direct contact membrane distillation, and a brine solution with the concentration of 3.5% is subjected to filtration test, so that an excellent desalting effect is obtained, and the advantages brought by the unique structural characteristic of the honeycomb porous super-hydrophobic separation layer are highlighted.
Compared with the prior art, the invention has the beneficial effects that:
(1) the product is efficient and durable, the preparation method is simple and easy to implement, the price is low, the solvent is convenient to recycle, and the operation of large-scale production is easy to realize;
(2) the super-hydrophobic nanofiber composite membrane for membrane distillation, which is obtained by the invention, has unique structural characteristics, can obviously improve the defects of low porosity, low vapor flux and easy wetting of membrane pores of the traditional membrane distillation membrane, so that the membrane distillation technology can be further developed in the field of seawater desalination.
Drawings
FIG. 1 is an electron microscope image of the field emission surface of the nanofiber composite membrane prepared in example 1;
FIG. 2 is an electron microscope image of the field emission cross section of the nanofiber composite membrane prepared in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of a super-hydrophobic nanofiber composite membrane for membrane distillation comprises the following steps:
(1) dissolving 15g of polyvinylidene fluoride (PVDF) in 85g N, N-Dimethylformamide (DMF), and stirring at constant temperature for 24h in an oil bath kettle at 80 ℃ to obtain a uniform and transparent electrostatic spinning solution. Dissolving 0.3g of atactic polypropylene in 99.7g of dimethylbenzene, stirring for 5 hours in an oil bath kettle at the temperature of 99 ℃ at constant temperature to obtain a uniform and transparent suction filtration solution, and then cooling to 60 ℃ at the temperature of 30 ℃ for later use;
(2) adding the electrostatic spinning stock solution obtained in the step (1) into a container, controlling the extrusion rate by a micro-injection pump, wherein the extrusion rate of the solution is 5 mu L/min, a needle is connected with a high-voltage electrode, the voltage is 28kV, the receiving distance is 15cm, the relative air humidity is 36%, the ambient temperature is 31 ℃, the rotating speed of a receiving roller is 800r/min, and carrying out electrostatic spinning to obtain polyvinylidene fluoride electrostatic spinning nanofibers with the average diameter of 320 nm;
(3) and (3) carrying out hot pressing treatment on the polyvinylidene fluoride nano-fiber porous membrane prepared in the step (2), wherein the temperature of a heating plate is 165 ℃, the pressure is 0.01MPa, and the heat treatment time is 10 min. The thickness of the nanofiber membrane after the hot-pressing treatment is 100 mu m;
(4) and (2) cooling the solution (1) to be 10g of suction filtration solution at the temperature of 60 ℃, carrying out vacuum suction filtration under negative pressure (-0.1MPa) to ensure that the gelatinized random polypropylene is deposited on the surface of the porous support layer of the nano fiber, removing the solvent-rich phase and collecting the solvent-rich phase in a suction filtration bottle. Stopping suction filtration when no redundant solution exists on the surface of the membrane, adding a certain amount of volatile polyolefin non-solvent isopropanol, standing for a period of time, and suction-filtering off the non-solvent to form the random polypropylene porous skin layer. The prepared super-hydrophobic nano-fiber porous composite membrane is subjected to heat treatment for 12 hours in an oven with the temperature of 60 ℃ and the vacuum degree of-0.1 Mpa, and the super-hydrophobic porous membrane for membrane distillation is obtained. The field emission surface electron micrograph is shown in FIG. 1, and the field emission cross-sectional electron micrograph is shown in FIG. 2;
(5) the prepared product membrane is used for evaluating the desalting performance in a direct contact membrane distillation test, and a NaCl aqueous solution with the concentration of 3.5 wt% is subjected to a filtration test, wherein the temperature of cold-side deionized water (the conductivity is less than 5 mu s/cm) is 20 ℃, the temperature of hot-side NaCl solution is 60 ℃, the flow rates of cold-side liquid and hot-side liquid are both 0.6 mu L/min before the high desalting rate of 99.99% is ensuredUnder the premise that the conductivity of the cold-side deionized water is always kept below 5 mu s/cm, the water vapor flux is 55.6 kg.m-2·h-1The product membrane is capable of maintaining efficient salt rejection and water vapor flux over a run time range of up to 50 hours.
Example 2
A preparation method of a super-hydrophobic nanofiber composite membrane for membrane distillation comprises the following steps:
(1) 20g of poly (vinylidene fluoride-co-hexafluoropropylene) was dissolved in 80g N, N-dimethylacetamide as a spinning solution, and stirred in an oil bath pan at 40 ℃ for 24 hours at a constant temperature to obtain a uniform and transparent electrostatic spinning solution. Dissolving 0.3g of polyethylene in 99.7g of dimethylbenzene, stirring for 5 hours at constant temperature in an oil bath kettle at 99 ℃ to obtain a uniform and transparent suction filtration solution, and then cooling to 50 ℃ at 30 ℃ for later use;
(2) respectively adding the electrostatic spinning stock solution obtained in the step (1) into containers, controlling the extrusion rate by a micro-injection pump, wherein the extrusion rate of the solution is 5 mu L/min, an eccentric needle is connected with a high-voltage electrode, the voltage is 25kV, the receiving distance is 15cm, the relative humidity of air is 32%, the ambient temperature is 30 ℃, the rotating speed of a receiving roller is 700r/min, and carrying out electrostatic spinning to obtain poly (vinylidene fluoride-co-hexafluoropropylene) electrostatic spinning nanofibers with the average diameter of 680 nm;
(3) and (3) carrying out hot-pressing treatment on the poly (vinylidene fluoride-co-hexafluoropropylene) nano fiber porous membrane prepared in the step (2), wherein the temperature of a heating plate is 150 ℃, the pressure is 0.01MPa, and the heat treatment time is 15 min. The thickness of the nanofiber membrane after the hot-pressing treatment is 100 mu m;
(4) and (2) cooling the solution (1) to 10g of suction filtration solution at the temperature of 50 ℃, carrying out vacuum suction filtration under negative pressure (-0.1MPa) to deposit the gelatinized polyethylene on the surface of the nanofiber porous support layer, removing the solvent-rich phase, and collecting the solvent-rich phase in a suction filtration bottle. Stopping suction filtration when no redundant solution exists on the surface of the membrane, adding a certain amount of volatile polyolefin non-solvent butanone, standing for a period of time, and suction-filtering off the non-solvent to form a polyethylene porous skin layer. The prepared super-hydrophobic nano-fiber porous composite membrane is subjected to heat treatment for 12 hours in an oven with the temperature of 60 ℃ and the vacuum degree of-0.1 Mpa, and the super-hydrophobic porous membrane for membrane distillation is obtained;
(5) the prepared product membrane is used for evaluating the desalting performance in a direct contact membrane distillation test, a NaCl aqueous solution with the concentration of 3.5 wt% is subjected to a filtration test, wherein the temperature of cold-side deionized water (the conductivity is less than 5 mu s/cm) is 20 ℃, the temperature of hot-side NaCl solution is 80 ℃, the liquid flow rates of cold and hot sides are all 0.6 mu L/min, the conductivity of the cold-side deionized water is always maintained below 5 mu s/cm under the premise of ensuring the high desalting rate of 99.99%, and the water vapor flux is 130.8 kg.m-2·h-1The product membrane maintains efficient salt rejection and water vapor flux over a run time range of up to 50 hours.
Example 3
A preparation method of a super-hydrophobic nanofiber composite membrane for membrane distillation comprises the following steps:
(1) 8g of polyacrylonitrile was dissolved in 92g N, N-dimethylformamide, and stirred in an oil bath pan at 50 ℃ for 6 hours at a constant temperature to obtain a uniform and transparent electrospinning solution. Dissolving 0.6g of random polypropylene in 99.4g of cyclohexane, stirring for 5 hours in an oil bath kettle at the constant temperature of 95 ℃ to obtain a uniform and transparent suction filtration solution, and then cooling to 30 ℃ at the temperature of 20 ℃ for later use;
(2) adding the electrostatic spinning stock solution in the step (1) into a container, controlling the extrusion rate by a micro-injection pump, wherein the extrusion rate of the solution is 16 mu L/min, connecting a needle head with a high-voltage electrode, the voltage is 20kV, the receiving distance is 15cm, the air relative humidity is 36%, the ambient temperature is 31 ℃, the rotating speed of a receiving roller is 800r/min, and carrying out electrostatic spinning to obtain the polyacrylonitrile electrostatic spinning nanofiber with the average diameter of 250 nm;
(3) and (3) carrying out hot pressing treatment on the polyacrylonitrile nano fiber porous membrane prepared in the step (2), wherein the temperature of a heating plate is 100 ℃, the pressure is 0.05MPa, and the heat treatment time is 5 min. The thickness of the nanofiber membrane after the hot-pressing treatment is 100 mu m;
(4) and (2) cooling the solution (1) to 10g of suction filtration solution at the temperature of 30 ℃, carrying out vacuum suction filtration under negative pressure (-0.1MPa) to deposit the gelatinized random polypropylene on the surface of the nanofiber porous support layer, removing the solvent-rich phase, and collecting the solvent-rich phase in a suction filtration bottle. Stopping suction filtration when no redundant solution exists on the surface of the membrane, adding a certain amount of volatile polyolefin non-solvent ethanol, standing for a period of time, and suction-filtering off the non-solvent to form the random polypropylene porous skin layer. The prepared super-hydrophobic nano-fiber porous composite membrane is subjected to heat treatment for 12 hours in an oven with the temperature of 60 ℃ and the vacuum degree of-0.1 Mpa, and the super-hydrophobic porous membrane for membrane distillation is obtained;
(5) the prepared product membrane is used for evaluating the desalting performance in a direct contact membrane distillation test, a NaCl aqueous solution with the concentration of 3.5 wt% is subjected to a filtration test, wherein the temperature of cold-side deionized water (the conductivity is less than 5 mu s/cm) is 20 ℃, the temperature of hot-side NaCl solution is 60 ℃, the liquid flow rates of cold and hot sides are all 0.6 mu L/min, the conductivity of the cold-side deionized water is always maintained below 5 mu s/cm under the premise of ensuring the high desalting rate of 99.99%, and the water vapor flux is 55.6 kg.m-2·h-1The product membrane is capable of maintaining efficient salt rejection and water vapor flux over a run time range of up to 30 hours.
Example 4
A preparation method of a super-hydrophobic nanofiber composite membrane for membrane distillation comprises the following steps:
(1) 18g of polyvinylidene fluoride (PVDF) is dissolved in 82g N, N-Dimethylformamide (DMF), and the mixture is stirred for 24 hours at a constant temperature in an oil bath kettle at 80 ℃ to obtain a uniform and transparent electrostatic spinning solution. Dissolving 0.3g of isotactic polypropylene in 99.7g of dimethylbenzene, stirring for 6 hours in an oil bath kettle at the constant temperature of 100 ℃ to obtain a uniform and transparent suction filtration solution, and then cooling to 75 ℃ at the temperature of 40 ℃ for later use;
(2) adding the electrostatic spinning stock solution obtained in the step (1) into a container, controlling the extrusion rate by a micro-injection pump, wherein the extrusion rate of the solution is 5 mu L/min, a needle is connected with a high-voltage electrode, the voltage is 30kV, the receiving distance is 15cm, the relative air humidity is 36%, the ambient temperature is 31 ℃, the rotating speed of a receiving roller is 800r/min, and carrying out electrostatic spinning to obtain polyvinylidene fluoride electrostatic spinning nanofibers with the average diameter of 400 nm;
(3) and (3) carrying out hot pressing treatment on the polyvinylidene fluoride nano-fiber porous membrane prepared in the step (2), wherein the temperature of a heating plate is 165 ℃, the pressure is 0.01MPa, and the heat treatment time is 10 min. The thickness of the nanofiber membrane after the hot pressing treatment is 100 mu m;
(4) and (2) cooling the solution (1) to be filtered at room temperature to be 10g at 75 ℃, carrying out vacuum filtration under negative pressure (-0.1MPa) to ensure that the gelatinized isotactic polypropylene is deposited on the surface of the porous supporting layer of the nano-fiber, removing the solvent-rich phase and collecting the solvent-rich phase in a filtration bottle. Stopping suction filtration when no redundant solution exists on the surface of the membrane, adding a certain amount of volatile polyolefin non-solvent isopropanol, standing for a period of time, and suction-filtering off the non-solvent to form the isotactic polypropylene porous skin layer. The prepared super-hydrophobic nano-fiber porous composite membrane is subjected to heat treatment for 12 hours in an oven with the temperature of 60 ℃ and the vacuum degree of-0.1 Mpa, and the super-hydrophobic porous membrane for membrane distillation is obtained;
(5) the prepared product membrane is used for evaluating the desalting performance in a direct contact membrane distillation test, a NaCl aqueous solution with the concentration of 3.5 wt% is subjected to a filtration test, wherein the temperature of cold-side deionized water (the conductivity is less than 5 mu s/cm) is 20 ℃, the temperature of hot-side NaCl solution is 60 ℃, the liquid flow rates of cold and hot sides are all 0.6 mu L/min, the conductivity of the cold-side deionized water is always maintained below 5 mu s/cm under the premise of ensuring the high desalting rate of 99.99%, and the water vapor flux is 61.3 kg.m-2·h-1The product membrane is capable of maintaining efficient salt rejection and water vapor flux over a run time range of up to 40 hours.
Claims (6)
1. The preparation method of the super-hydrophobic nanofiber composite membrane for membrane distillation is characterized by comprising the following steps of:
step 1): preparing a base layer by adopting a polymer solution electrostatic spinning method, and then carrying out hot pressing treatment, wherein the temperature of a hot pressing plate is 50-500 ℃, and the pressure is 1 kPa-6 multiplied by 104kPa, the hot pressing time is 30 s-5 h, so that a connection point is formed by remelting at a cross point between adjacent fibers, and the fluffy nanofiber membrane is complete and uniform;
step 2): preparing a porous super-hydrophobic separation layer: heating and dissolving a polyolefin material in a solvent, uniformly stirring, cooling to different temperatures at a controllable cooling rate, combining the principle that the polyolefin solution is in a thermodynamically unstable state and is easy to gelate, and removing a solvent-rich phase under the external action force of a vacuum-assisted suction filtration method, wherein the polymer-rich phase is deposited on the surface of the base layer obtained in the step 1); stopping suction filtration when no redundant solution exists on the surface of the membrane, adding a volatile polyolefin non-solvent, standing, and suction-filtering off the polyolefin non-solvent to construct a nanofiber composite membrane with a porous structure skin layer on a microscale;
step 3): carrying out heat treatment on the nanofiber composite membrane obtained in the step 2) for 8-24h in an oven with the temperature of 35-80 ℃ and the vacuum degree of-0.09-0.1 MPa.
2. The method for preparing the superhydrophobic nanofiber composite membrane for membrane distillation according to claim 1, wherein the nanofiber composite membrane has a porosity of 75 to 95%, a thickness of 50 to 300 μm, an average pore diameter of 0.1 to 1.5 μm, a pore size distribution of 0.11 to 4.0 μm, a water osmotic pressure of 0.4 to 3bar, and a water contact angle of 140 to 175 °.
3. The method for preparing the superhydrophobic nanofiber composite membrane for membrane distillation as claimed in claim 1, wherein the solute adopted in the polymer solution of the step 1) is one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethylmethacrylate, polyvinyl chloride, polyurethane, polycarbonate, polystyrene, polyacrylonitrile or polyether sulfone, and the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, dichloromethane, trichloromethane, acetone, benzene, toluene, cyclohexane and dimethyl sulfoxide.
4. The preparation method of the superhydrophobic nanofiber composite membrane for membrane distillation as claimed in claim 1, wherein the specific process parameters of the electrospinning method in the step 1) are as follows: the concentration of the polymer solution is 2-40 wt%, the voltage is 10-35 kV, the extrusion pushing speed of the solution is 2-30 mu L/min, the receiving distance is 10-30 cm, the rotating speed of a receiving roller is 300-1000 r/min, the atmosphere of the spinning environment is a closed or open space system, the relative humidity of the system is 10-40%, and the temperature is 15-45 ℃.
5. The method for preparing the superhydrophobic nanofiber composite membrane for membrane distillation as claimed in claim 1, wherein the polyolefin material in the step 2) is any one or more of polypropylene, polyethylene, polybutylene and poly-4-methyl-1-pentene; the solvent is any one or more of dimethylbenzene, normal hexane, cyclohexane, decalin, tetrahydronaphthalene and petroleum ether; the polyolefin non-solvent is any one or more of isopropanol, ethanol, methanol and butanone.
6. The preparation method of the superhydrophobic nanofiber composite membrane for membrane distillation as claimed in claim 1, wherein the negative pressure adopted by the vacuum assisted suction filtration method in the step 2) is-0.09 MPa to-0.1 MPa, and the loading amount of polyolefin is 0.1-500 g/m2。
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